CAPITULO 4. TERMODINAMICA FUERA DEL EQUILIBRIO.

CAPITULO 4. TERMODINAMICA FUERA DEL EQUILIBRIO.

4.1 FUNDAMENTOS GENERALES.

4.2 SEGUNDA LEY PARA SISTEMAS FUERA DEL EQUILIBRIO. 4.3 TERMODINAMICA FUERA DEL EQUILIBRIO EN SISTEMAS LINEALES.

4.1 FUNDAMENTOS GENERALES. EQUILIBRIO: Se dice que un sistema esta en equilibrio cuando tiene una energa libre mnima. Se dice que un sistema aislado est en equilibrio qumico si no suceden cambios en la composicin qumica del sistema. El criterio para el equilibrio qumico se basa en la segunda ley de la termodinmica, y para un sistema a una temperatura y presin especificas puede expresarse como:

dG T , P 0

Para la reaccin:

v A A vB B vC C vD D
Donde las v son los coeficientes estequiomtricos, el criterio de equilibrio qumico puede expresarse en trminos de las funciones de Gibbs como:

vC G C vD G D v A G A vB G B 0
que es valida para cualquier reaccin qumica independientemente de la fase implicada.

SOLID-LIQUID PHASE DIAGRAMS: TIN AND LEAD

Cooling curves for pure substances

Suppose you have some pure molten lead and allow it to cool down until it has all solidified, plotting the temperature of the lead against time as you go. You would end up with a typical cooling curve for a pure substance.

Cooling curves for tin-lead mixtures

If you add some tin to the lead, the shape of the cooling curve changes. The next graph shows what happens if you cool a liquid mixture containing about 67% lead and 33% tin by mass.

Cooling curves for tin-lead mixtures

If you had less tin in the mixture, the overall shape of the curve stays much the same, but the point at which the lead first starts to freeze changes. The less tin there is, the smaller the drop in the freezing point of the lead. For a mixture containing only 20% of tin, the freezing point of the lead is about 275C. That's where the graph would suddenly become less steep. BUT . . . you will still get the graph going horizontal (showing the freezing of both the tin and lead) at exactly the same temperature: 183C.

Cooling curves for tin-lead mixtures

As you increase the proportion of tin, the first signs of solid lead appear at lower and lower temperatures, but the final freezing of the whole mixture still happens at 183C. That continues until you have added enough tin that the mixture contains 62% tin and 38% lead. At that point, the graph changes.

Cooling curves for tin-lead mixtures

This particular mixture of lead and tin has a cooling curve which looks exactly like that of a pure substance rather than a mixture. There is just the single horizontal part of the graph where everything is freezing. However, it is still a mixture. If you use a microscope to look at the solid formed after freezing, you can see the individual crystals of tin and lead. This particular mixture is known as a eutectic mixture. The word "eutectic" comes from Greek and means "easily melted". The eutectic mixture has the lowest melting point (which is, of course, the same as the freezing point) of any mixture of lead and tin. The temperature at which the eutectic mixture freezes or melts is known as the eutectic temperature.

What happens if there is more than 62% of tin in the mixture?

You can trace it through in exactly the same way, by imagining starting with pure tin and then adding lead to it. The cooling curve for pure liquid tin looks like this: It`s just like the pure lead cooling curve except that tin's freezing point is lower.

What happens if there is more than 62% of tin in the mixture?

If you add small amounts of lead to the tin, so that you have perhaps 80% tin and 20% lead, you will get a curve like this:

Notice the lowered freezing point of the tin. Notice also the final freezing of the whole mixture again takes place at 183C. As you increase the amount of lead (or decrease the amount of tin - same thing!) until there is 62% of tin and 38% of lead, you will again get the eutectic mixture with the curve we've already looked at.

Notice the lowered freezing point of the tin. Notice also the final freezing of the whole mixture again takes place at 183C. As you increase the amount of lead (or decrease the amount of tin - same thing!) until there is 62% of tin and 38% of lead, you will again get the eutectic mixture with the curve we've already looked at.

The phase diagram

Constructing the phase diagram You start from data obtained from the cooling curves. You draw a graph of the temperature at which freezing first starts against the proportion of tin and lead in the mixture. The only unusual thing is that you draw the temperature scale at each end of the diagram instead of only at the left-hand side.

Notice that at the left-hand side and right-hand sides of the curves you have the freezing points (melting points) of the pure lead and tin.

The phase diagram

To finish off the phase diagram, all you have to do is draw a single horizontal line across at the eutectic temperature. Then you label each area of the diagram with what you would find under the various different conditions.

Figura x. Gibbs energy curves to construct a binary phase diagram that shows miscibility in both the liquid and the solid

Figura y. Uso de las curvas de energa de Gibbs para construir un diagrama de fase binario del tipo eutctico.

Cristalizacin de un metal puro

Crystallization is transformation of liquid phase to solid crystalline phase. There are two general stages of phase transformation (crystallization) process nucleation and growth:

Cristalizacin de un metal puro

1. Nucleation Nucleation is a process of formation of stable crystallization centers of the new phase. Nucleation may occur by either homogeneous or heterogeneous mechanism, depending on the value of undercooling of the liquid phase (cooling below the equilibrium freezing point). Presence of foreign particles or other foreign substance in the liquid alloy (walls of the casting mold) enables to initiate crystallization at minor value of undercooling (few degrees below the freezing point). This is heterogeneous nucleation. If there is no solid substance present, undercooling of a hundred degrees is required in order to form stable nuclei or seeds crystals, providing following crystal growth (homogeneous nucleation)

Cristalizacin de un metal puro

2. Crystal growth Number of stable nuclei per unit volume of crystallizing alloy determines the grain size. When a large number of stable nuclei are present in chill zone of mold, fine equiaxed grains form. Latent crystallization heat, liberating from the crystallizing metal, decreases the undercooling of the melt and depresses the fast grains growth. At this stage some of small grains, having favorable growth axis, start to grow in the direction opposite to the direction of heat flow. As a result columnar crystals (columnar grains) form. Contrary to the pure metals, in alloys different type of undercooling takes place. It is called constitutional undercooling.

Constitutional undercooling. Since solubility of an alloying element in solid is lower, than in liquid at the same temperature, this element (solute) is rejected by the solidifying metal to the liquid phase, enriching the region of liquid adjacent to the crystallization front. For the most of the alloys: the higher the concentration of alloying element in the alloy, the lower its liquidus temperature (temperature at which crystallization of the alloy starts). Thus crystallization temperature of the liquid, adjacent to the crystallization front, rises with increasing the distance from the front surface. Therefore there is a layer of the liquid, where its temperature is lower, than its crystallization temperature. This is the region of constitutional undercooling (see the figure below).

Cristalizacin de un metal puro

Figura z. This figure represents the development of microstructure during the equilibrium solidification of a 35 wt% Ni - 65 wt% Cu alloy.

Figura z. Portion of a binary phase diagram containing a two-phase liquid-plus-solid field illustrating (a) application of the lever rule to (b) equilibrium freezing, (c) nonequilibrium freezing, and (d) heating of a homogenized sample.1

Figure 1. El diagrama de equilibrio de fases Fe-C. Se muestra la microestructura de un acero al carbono lentamente enfriado teniendo una composicin Co.

Figure 1. El diagrama de equilibrio de fases Fe-C.

Microestructuras de los aceros en equilibrio

Microestructuras de los aceros en equilibrio

0.3 % C 0.6 % C 0.8 % C 1.1 % C

Enfriamiento de no equilibrio.

Cuando una aleacin es enfriada rpidamente, pueden ocurrir varios cambios en la microestructura: Las fases de equilibrio pueden verse a temperatura ambiente, pero su morfologa (forma) puede ser diferente. La microestructura de altas temperaturas puede congelarse, y ella puede observarse a temperatura ambiente. Puede aparecer una fase completamente nueva, la cual no esta presente en el diagrama de equilibrio de fases.

Enfriamiento de no equilibrio.

Para velocidades de enfriamiento rpidas, los diagramas de equilibrio no pueden ser usados. En este caso, son necesarios los diagramas TTT (transformacion tiempo-temperatura). La figure 2 muestra un diagrama hipottico TTT. Sobre el diagrama se sobreimponen varias velocidades de enfriamiento. La velocidad de enfriamiento mas lenta es enfriamiento en el horno, en el cual el material es dejado en el horno y la potencia es desconectada. Asi, el material es enfriado hasta temperatura ambiente dentro del horno. El enfriamiento en aire es algo mas rpido que el enfriamiento en el horno. Cuando el material es sacado del horno y enfriado en aire hasta temperatura ambiente, llamamos a esto enfriamiento en aire. La velocidad de enfriamiento mas rpida es obtenida por templado en agua. En el templado, el material es sacado del horno e inmediatamente sumergido en agua. El medio de templado puede ser aceite o agua, pero mas rpida velocidad de enfriamiento es obtenida con agua.

Figure 2. Curvas de enfriamiento sobre un diagrama TTT hipotetico de un acero al carbono.

En el enfriamiento al horno, la velocidad de enfriamiento es muy lenta y puede considerarse que se satisfacen las condiciones de equilibrio. Por lo tanto, el material sigue los limites de fase en el diagrama de equilibrio de fases. En el enfriamiento en aire, la velocidad de enfriamiento es mas rpida. Para aceros al carbono, el diagrama de fases es todava valido, y se puede ver las fases predichas por el diagrama de fases. Solo cambian la morfologa y cantidad relativa de las fases. La razn para esto es el mayor DT (T-TE), la cantidad de sobreenfriamiento. Como DT es mas efectiva sobre la velocidad de nucleacin en comparacin a la velocidad de crecimiento, se esperan granos mas finos para mayores velocidades de enfriamiento. En el templado en agua, puede aparecer una fase completamente nueva. Por ejemplo, en aleaciones ferrosas, la austenita se transforma a martensita, si el enfriamiento es bastante rpido. La martensita tiene una estructura parecida a agujas y es muy dura.

Microestructuras de los aceros fuera de equilibrio

Effect of Alloying Elements

Figure 3.a shows a typical TTT diagram for a plain carbon steel. The addition of carbon and alloying elements effect several parameters in TTT diagrams, such as the shape, martensite start temperature and relative position of the curve. In Figure 3.b, the effect of a small amount of Cr is seen. The TTT curve is shifted to right. The higher the percentage of Cr, the larger becomes this shift. Therefore, transformation of austenite to martensite becomes easier in alloy steels.

Figure 3. The schematic representation of the effect of alloying elements on the TTT curve of a eutectoid steel.